Dehydrochlorination of Poly(viny1 Chloride) in Pyridine. III. Thermal and Mechanical Properties

The thermal properties of dehydrochlorinated PVC (DHPVC) were evaluated. From thermogravimetric analysis (TGA) and differential thermal analysis (DTA), a larger decrease in thermal stability of dehydrochlorinated PVC than of PVC was observed. Thermal stability of DHPVC increased continuously with an increase in dehydrochlorination temperature and dilution of the reaction solution during dehydrochlorination. However, with an increase in dehydrochlorination time, an increase in thermal stability after an initial drop was obtained. The highly cross-linked product separated from the reaction solution at higher dehydrochlorination temperatures showed a lower thermal stability than that of corresponding soluble DHPVC. The stress-strain behavior of dehydrochlorinated PVC samples was also studied.     

Dehydrochlorination of Poly(vinyl Chloride) in Pyridine. 1. Effect of Conditions

Poly(viny1 chloride) (PVC) was dehydrochlorinated thermally in pyridine solution under N₂ atmosphere and the effect of variation of reaction time, temperature, and concentration of PVC in pyridine was studied. The extent of dehydrochlorination (or conversion, x%) increases with an increase in reaction time and temperature, and with a decrease in the concentration of PVC. Incomplete precipitation of dehydrochlorinated PVC (DHPVC) occurs by nonsolvent (methanol). During dehydrochlorination there is no HCl evolution as it forms a pyridine hydrochloride complex which is supposed to act as a catalyst for dehydrochlorination. A possible mechanism has been proposed. Chain scission and cross-linking reactions are responsible for the molecular weight changes that take place during the reaction.     

Kinetics of the dehydrochlorination of poly(vinyl chloride) in the presence of NaOH and various diols as solvents

The dehydrochlorination of PVC in the presence of NaOH was investigated in different diols. Diethylene glycol (DEG), triethylene glycol (TEG), and propylene glycol (PG) were found to be effective in accelerating the dechlorination of PVC. The dehydrochlorination was promoted in the order TEG > DEG > PG, which was in agreement with the compatibility between PET and the diol. Compatibility resulted in an improved penetration of the PVC particle by the solvent, leading to the acceleration of the dehydrochlorination. The dehydrochlorination of PVC in NaOH/diol followed first-order kinetics, confirming the progress of the reaction under chemical reaction control. The apparent activation energies were 82 kJ mol⁻¹, 109 kJ mol⁻¹, and 151 kJ mol⁻¹ for TEG, DEG, and PG, respectively. The lower the activation energy became the faster the dehydrochlorination of PVC proceeded.     

Degradation of chlorinated polyethylene. I. Effect of antimony oxide on the rate of dehydrochlorination

The degradation of two chlorinated polyethylene compounds CPE 25 (45% chlorine) and CPE 16 (36% chlorine) was studied by following their rates of dehydrochlorination at two temperatures, 150°C and 180°C in pure nitrogen and pure oxygen atmospheres. Studies on the powdered polymers showed that the dehydrochlorination rate of CPE 25 is about fourteen times faster than that of CPE 16 in nitrogen atmospheres and only three to four times faster in oxygen. The molded polymers gave a lower rate of dehydrochlorination than when in the powdered form. This effect is attributed to diffusion factors. The antimony oxide brought about an induction period in the dehydrochlorination reaction during which only a small amount of HCl is evolved, followed by a very fast rate of dehydrochlorination both in oxygen and nitrogen atmospheres. The duration of the induction period increases with increase in the Sb₂O₃ concentration, but is followed by an accelerated HCl loss which is faster when Sb₂O₃ concentration is higher. This work provides supporting evidence that SbCl₃ was formed and lost during degradation. Mechanisms of dehydrochlorination are suggested for the reaction in the case of pure chlorinated polyethylene and for the polymer containing antimony oxide.     

氯化天然橡胶的等速升温热降解动力学

天然胶乳;氯化天然橡胶的等速升温热降解动力学     

Kinetics of the Alkaline Dehydrochlorination of Polyvinyl Chloride)

From previous investigations of the alkaline dehydrochlorination of PVC it is well known that polyene sequences are formed. In this paper the true overall kinetics of the dehydrochlorination reaction between PVC and alcoholic KOH in tetrahydrofuran solution was studied at 9.5°C by measuring the rate of disappearance of KOH. Titrations of the hydroxide ions consumed and the chloride ions evolved showed close agreement. IR spectra of the samples did not show any evidence of substitution by hydroxide ions. Small amounts of DMSO present in the solvent were found to increase the reaction rate markedly. The kinetic scheme was discussed and the first rate constant was determined. Preliminary results of reactions of the polyene sequences with various reagents are presented. These reactions were made in order to introduce new functional groups into the PVC chains.     

Thermal degradation of polymer-fire retardant mixtures—Part II: Mechanism of interaction in polypropylene-chlorinated paraffin mixtures

The thermal degradation of polypropylene is accelerated when it is heated in mixtures with a fire retardant chlorinated paraffin (Cl 70%) whose dehydrochlorination rate is simultaneously reduced.The mechanism proposed to account for this behaviour involves the attack of the chlorine atoms, which propagate the dehydrochlorination reaction, on the tertiary hydrogen atoms of polypropylene with formation of HCl. The kinetic chain length of the dehydrochlorination is decreased and the rate of evolution of HCl is lowered, while the radicals formed on the polypropylene chain lead to its scission and volatilisation.The effects of these reactions on the fire retardant performance of the mixture are discussed.     

Continuous dehydrochlorination of 1,3-dichloropropan-2-ol to epichlorohydrin: process parameters and by-products formation

The influence of pre-reactor and reactor temperatures on the conversion of 1,3-dichloropropan-2-ol and the selectivity of its transformation to epichlorohydrin in continuous dehydrochlorination for two modes of the reaction product collection was studied. The dehydrochlorination process and mechanism of diglycidyl ether formation are described.     

Effect of ozone on poly(vinyl chloride) degradation

The influence of ozone on the kinetics and mechanisms of poly(vinyl chloride) degradation has been studied. The rate constants for reaction of ozone with saturated and unsaturated units of macromolecules have been measured. The products of the reaction of ozone with double bonds are inactive and do not influence the subsequent thermal dehydrochlorination of the polymer. The products of reaction of ozone with saturated units greatly increase dehydrochlorination.     

Photodehydrochlorination of carbon monoxide–vinyl chloride copolymer

In order to examine effect of the carbonyl group in carbon monoxide–vinyl chloride copolymer, poly(CO–VC), photoirradiation with a high-pressure mercury lamp on the copolymer was carried out. Poly(CO–VC) had a rate of dehydrochlorination three times that of PVC, and the reaction involved a decrease in chlorine content. Also there was a marked change in the ultraviolet spectra of the photoirradiated films. However, no pronounced change of molecular weight was observed, but a change in R_f in TLC was observed clearly. These facts confirmed that photoirradiation of poly(CO–VC) produced a structural change by dehydrochlorination without serious decrease of molecular weight. In addition, photodehydrochlorination of the copolymer or PVC film was followed kinetically, and after ozonolysis of the dehydrochlorinated polymers, the number-average molecular weights were measured. From the results of degree of dehydrochlorination and molecular weight, the number average of conjugated double bonds or carbonyl groups was estimated. A mechanism for dehydrochlorination process by photo-irradiation is suggested.     

Poly(vinyl chloride) stabilisation with organo-tin compounds—Part II: Catalysis of the dehydrochlorination by butyl-tin chlorides

The catalytic effect of the various butyl-tin chlorides on the dehydrochlorination reaction of chlorohexene, used as a model compound for allylic chlorides in poly(vinyl chloride), has been studied in tetrahydrofuran and dichloroethane solutions. The reaction follows an E2 mechanism, the rate determining step being the formation of a delocalised allylic carbocation. The catalytic power is directly related to the Lewis acidity of the tin chlorides and, further, RSnCl₃ is comparable with ZnCl₂, although it is more sensitive to complexing with weak Lewis bases. In the presence of poly(vinyl chloride) at 180°C, these butyl-tin chlorides show a retardation effect on dehydrochlorination, superimposed on a catalytic effect which increases with the Lewis acidity; however, in these conditions, RSnCl₃ is much less efficient than ZnCl₂ in catalysing the dehydrochlorination reaction.     

Mechanism of the thermal dehydrochlorination of poly(vinyl chloride) models in the liquid phase

The thermal dehydrochlorination of model compounds of PVC has been investigated in the liquid phase in an inert atmosphere. Electrophilic catalysis and the effect of various solvents on this reaction have been studied. It has been found that the electron-accepting power of the reaction medium is the decisive rate-determining factor, while the dielectric constant comes second. A mechanism of thermal dehydrochlorination has been suggested, in which a reaction between the substrate and the proton giving rise to the carbonium ion is the rate-determining step for the whole process.     

Dehydrochlorination reactions in polymers. Part II. Chlorinated polystyrene

The dehydrochlorination of chlorinated polystyrene was studied in the temperature range 120–220°C., when HCl was the sole volatile product. The dehydrochlorination was accompanied by the slow development of color and chain scission. The elimination rate fell too rapidly with reaction extent to be accounted for by reduction of reagent. Solution studies in o-dichlorobenzene indicated that the reaction was initially first-order in polymer concentration but was retarded by the polyene reaction products. The overall elimination was interpreted as a radical process in which the product was an active retarder. These observations are also valid for the elimination of HBr from brominated polystyrene.     

M/C3N4/AC (M=Au,Pt,Ru)催化乙炔与二氯乙烷耦合反应:双功能催化剂性能如何?

聚氯乙烯是世界上产量最大的通用塑料,在日常生活的诸多领域具有广泛应用.按照原料来源划分,聚氯乙烯的工业生产方法主要有基于煤炭的电石法和基于石油的"平衡法".我国有丰富的煤炭资源,因此,电石乙炔法是合成聚氯乙烯的主要途径.该方法采用乙炔与氯化氢在活性炭担载氯化汞催化剂上进行氢氯化反应得到聚氯乙烯的单体氯乙烯.然而,由于汞...     

The thermal degradation of polychloroprene-III degradation of polychloroprene/poly(methyl methacrylate) mixtures

The mechanism of dehydrochlorination has been studied by examining the degradation of polychloroprene/poly(methyl methacrylate) blends, using thermal volatilization analysis and infrared spectroscopy; the behaviour has been compared with that previously found for PVC/PMMA blends. Unlike the latter system, the polychloroprene blends did not show any increased production of methyl methacrylate monomer in the early stages of breakdown. The stabilization effect on PMMA due to reaction of ester groups with hydrogen chloride, on the other hand, is much more evident in the case of polychloroprene blends than for PVC, PVC dehydrochlorination is retarded by the presence of PMMA, but evolution of hydrogen chloride from polychloroprene is unaffected to any significant extent. It is concluded that the dehydrochlorination of polychloroprene is not a radical chain process. A unimolecular mechanism is suggested.     

Effects of alkaline earth metal stearates on the dehydrochlorination of poly(vinyl chloride)

The thermo non-oxidative degradation of PVC and the effects of alkaline earth metal (Be, Mg, Ca, Ba) stearates were studied by thermogravimetry in the temperature range 150 to 500°C. The alkaline earth metal stearates were observed effectively reduce the dehydrochlorination of PVC. The synergistic effects of combinations of these salts with lead stearate were also studied and are discussed. Kinetic parameters such as the activation energy, order of reaction and Arrhenius factor were calculated by the Coats and Horowitz methods. The results showed that these metal stearates increase the activation energy required for the dehydrochlorination of PVC.     

Spectroscopic studies on the initial stages of thermal degradation of polychloroprene

Thermal degradation of polychloroprene under nitrogen, especially at the initial stages, has been studied by using ¹H-NMR, ¹³C-NMR and FT–IR spectroscopy. A model polymer of low molecular weight (M _n = 6300) was prepared to avoid gelation during degradation. None of isomerized 1,2 unit has been found in the original polymer. Allylic rearrangement of 1,2 unit was the first-stage reaction, which was finished within 30 min at 150°C. The extent of HCl loss was proportional to the decrease of isomerized 1,2 unit. It has been suggested that the next-stage reaction is dehydrochlorination of the isomerized 1,2 unit. The presence of terminal vinyl group and the increased amount of olefinic proton were not found in the degraded polymer. The back-biting mechanism involving a six-membered cyclization process is proposed for the dehydrochlorination. The thermal racemization has been also found to take place in the 3,4 unit.     

Chlorinated long-chain fatty acids. Their properties and reactions—VI : Kinetics and mechanisms of base-catalyzed dehydrochlorination of sodium threo,threo-9,10,12,13-tetrachlorooctadecanoate

The base-catalyzed dehydrochlorination of sodium threo,threo-9,10,12,13-tetra-chlorooctadecanoate has been carried out in aqueous ethylene glycol solutions. During the first reaction step two chlorine atoms are eliminated nearly simultaneously as hydrogen chloride whereas the third and fourth chlorine atoms are released separately. The relative rates of these three reaction steps at 130°C are 497,41 and 1, respectively. The possible reaction mechanisms have been discussed in light of the kinetic results and product analyses which showed that the dehydrochlorination results mainly in conjugated diene-yne systems.     

Benzofurans. Ketene intermediates in the perkin reaction

The intermediacy of ketenes in the intramolecular reaction of ketoacids with sodium acetate in acetic anhydride to form benzofurans is demonstrated. The Perkin reaction conditions are superior to the classical ketene generation method of triethylamine dehydrochlorination of the acid chloride.     

Thermal degradation of graft copolymers of PVC prepared by mastication with styrene and methyl methacrylate,and of further PVC mixtures and vinyl chloride copolymers

Graft copolymers prepared by mastication of PVC in the presence of styrene or of a styrene/ methyl methacrylate mixture, have been studied by thermogravimetry, estimation of hydrogen chloride, thermal volatilization analysis, and flash pyrolysis/g.l.c. The degradation behaviour of PVC/ polystyrene mixtures, vinyl chloride/styrene random copolymers, a random copolymer of methyl methacrylate and styrene, and PVC/poly-α-methylstyrene mixtures has also been studied. The graft copolymers resemble the PVC/methacrylate graft copolymers previously studied in showing retardation of the dehydrochlorination reaction, but contrast with them in yielding chain fragments but no monomer during HCl production. Some stabilization of the second component at higher temperatures is also found. PVC/polystyrene mixtures behave in the same way as the corresponding graft copolymers, but vinyl chloride/styrene copolymers show reduced stability towards both dehydrochlorination and monomer production compared with the homopolymers. PVC/poly-α-methylstyrene mixtures yield some monomer concurrently with HCl loss, and display marked retardation of the latter reaction. Stabilization of the second polymer at higher temperatures is again observed. Many of these results add further strong support to the view that chlorine atoms are involved as chain carriers in the thermal dehydrochlorination of PVC.